WO2014046256A1

WO2014046256A1 - Metallic foil having carrier

Info

Publication number: WO2014046256A1
Application number: PCT/JP2013/075557
Authority: WO
Inventors: 晃正森山
Original assignee: Jx日鉱日石金属株式会社
Priority date: 2012-09-20
Filing date: 2013-09-20
Publication date: 2014-03-27
Also published as: TWI615271B; TW201420332A; JPWO2014046256A1; JP6104260B2

Abstract

　Provided is a metallic foil having a carrier, wherein the peel strength of a resin sheet-shaped carrier and a metallic foil has been controlled. This metallic foil having a carrier, which comprises a sheet-shaped resin carrier and a metallic foil that has been detachably adhered to at least one surface of the carrier, is characterised in that the sheet-shaped carrier and the metallic foil are bonded using a resin coating comprising silicone and at least one resin selected from epoxy resin, melamine resin and fluororesin.

Description

Metal foil with carrier

The present invention relates to a metal foil with a carrier. More specifically, the present invention relates to a metal foil with a carrier used in the production of a single-sided or two-layer multilayer board or an ultra-thin coreless substrate used for a printed wiring board.

In general, a printed wiring board uses, as a basic constituent material, a dielectric material called “prepreg” obtained by impregnating a base material such as a synthetic resin plate, a glass plate, a glass nonwoven fabric, and paper with a synthetic resin. . Further, a sheet such as copper or copper alloy foil having electrical conductivity is bonded to the side facing the prepreg. The laminated body thus assembled is generally called a CCL (CopperoppClad Laminate) material. The surface of the copper foil in contact with the prepreg is usually a mat surface in order to increase the bonding strength. A foil made of aluminum, nickel, zinc or the like may be used instead of the copper or copper alloy foil. Their thickness is about 5 to 200 μm. This commonly used CCL (Copper Clad Laminate) material is shown in FIG.

Patent Document 1 proposes a metal foil with a carrier composed of a synthetic resin plate-shaped carrier and a metal foil that is mechanically peelably adhered to at least one surface of the carrier. Describes that it can be used for the assembly of printed wiring boards. It was shown that the peel strength between the plate-like carrier and the metal foil is preferably 1 gf / cm to 1 kgf / cm. According to the metal foil with a carrier, since the copper foil is supported over the entire surface by the synthetic resin, generation of wrinkles on the copper foil during lamination can be prevented. In addition, since the metal foil with carrier is in close contact with the synthetic resin without gaps, when the surface of the metal foil is plated or etched, it can be put into the chemical solution for plating or etching. . Furthermore, since the linear expansion coefficient of the synthetic resin is at the same level as the copper foil that is a constituent material of the substrate and the prepreg after polymerization, the circuit is not misaligned, resulting in fewer defective products, It has the outstanding effect that a yield can be improved.

JP 2009-272589 A

The metal foil with a carrier described in Patent Document 1 is an epoch-making invention that greatly contributes to reducing the manufacturing cost by simplifying the manufacturing process of the printed circuit board and increasing the yield, but the peel strength between the plate-like carrier and the metal foil. There is still room for further study on the optimization and means of the above. In particular, a remarkable problem for the inventor is that the peel strength between the plate-like carrier and the metal foil becomes too high depending on the material of the plate-like carrier, and means for easily adjusting the peel strength is provided. It is desirable. Then, this invention makes it a subject to provide the metal foil with a carrier in which the peeling strength of resin-made plate-shaped carrier and metal foil was adjusted.

As a result of intensive studies on the method for adjusting the peel strength between the resin plate and the metal foil, the present inventors combined at least one surface with a predetermined resin prior to bonding the resin plate and the metal foil. The present invention was completed by finding the possibility of realizing a peel strength according to the desired application by coating with a resin coating.

That is, the present invention is as follows.
(1) A metal foil with a carrier made of a resin-made plate-like carrier and a metal foil that is detachably adhered to at least one surface of the carrier, wherein the plate-like carrier and the metal foil are silicone, Metal foil with a carrier formed by bonding together using a resin coating film composed of any one or a plurality of resins selected from an epoxy resin, a melamine resin, and a fluororesin.
(2) The metal foil with a carrier according to (1), wherein the total amount of epoxy resin and melamine resin is included in the resin coating film in an amount of 10 to 1500 parts by mass with respect to 100 parts by mass of silicone.
(3) The metal foil with a carrier according to (1) or (2), wherein the resin coating film contains a fluororesin in an amount of 0 to 50 parts by mass with respect to 100 parts by mass of silicone.
(4) The metal foil with a carrier according to any one of (1) to (3), wherein the thickness of the resin coating film is 0.1 to 10 μm.
(5) The metal foil with a carrier according to any one of (1) to (4), wherein the peel strength between the plate-like carrier and the metal foil is 10 gf / cm or more and 200 gf / cm or less.
(6) The metal foil with a carrier according to any one of (1) to (5), wherein the resinous plate-like carrier contains a thermosetting resin.
(7) The metal foil with a carrier according to any one of (1) to (6), wherein the resin plate carrier is a prepreg.
(8) The metal foil with a carrier according to (6) or (7), wherein the resinous plate-shaped carrier has a glass transition temperature Tg of 120 to 320 ° C.
(9) The metal foil with a carrier according to any one of (1) to (8), wherein a ten-point average roughness (Rz jis) of a side surface in contact with the carrier of the metal foil is 3.5 μm or less.
(10) The ten-point average roughness (Rz jis) of the surface of the metal foil that is not in contact with the carrier is 0.4 μm or more and 10.0 μm or less, according to any one of (1) to (9) Metal foil with carrier.
(11) The metal foil with a carrier according to any one of (1) to (10), wherein the thickness of the metal foil is 1 μm or more and 400 μm or less.
(12) The peel strength between the metal foil and the plate-like carrier after heating at 220 ° C. for 3 hours, 6 hours or 9 hours is 10 gf / cm or more and 200 gf / cm or less (1) to (11) Metal foil with a carrier as described in any one of.
(13) The metal foil with a carrier according to any one of (1) to (12), wherein the metal foil is a copper foil.
(14) A metal foil for printed wiring board having a resin coating film composed of silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin, and a fluororesin on the surface of the metal foil .
(15) The metal foil for a printed wiring board according to (14), wherein the resin coating film includes a total of 10 to 1500 parts by mass of an epoxy resin and a melamine resin with respect to 100 parts by mass of silicone.
(16) The metal foil for printed wiring board according to (14) or (15), wherein the resin coating film contains a fluororesin in an amount of 0 to 50 parts by mass with respect to 100 parts by mass of silicone.
(17) The metal foil for printed wiring board according to any one of (14) to (16), wherein the resin coating film has a thickness of 0.1 to 10 μm.
(18) The resin coating is applied to the surface on which a resin coating film composed of the silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin, and a fluororesin is allowed to act. The metal foil for printed wiring board according to any one of (14) to (17), wherein a chromate treatment is performed before the film is applied.
(19) The printed wiring board according to any one of (14) to (18), wherein a ten-point average roughness (Rz jis) of a side surface in contact with the resin coating film of the metal foil is 3.5 μm or less. Metal foil.
(20) The ten-point average roughness (Rz jis) of the surface of the metal foil that is not in contact with the resin coating film is 0.4 μm or more and 10.0 μm or less. Metal foil for printed wiring boards as described.
(21) A metal foil having a resin coating film composed of at least one surface selected from silicone and an epoxy resin, a melamine resin, and a fluororesin on at least one surface, The metal foil used for the use which adheres the resin-made plate-shaped carrier in the said surface so that peeling is possible.
(22) The metal foil according to (21), wherein in the resin coating film, the total amount of epoxy resin and melamine resin is contained in an amount of 10 to 1500 parts by mass with respect to 100 parts by mass of silicone.
(23) The metal foil according to (21) or (22), wherein the resin coating film contains a fluororesin in an amount of 0 to 50 parts by mass with respect to 100 parts by mass of silicone.
(24) The metal foil according to any one of (21) to (23), wherein the resin coating film has a thickness of 0.1 to 10 μm.
(25) The resin coating is applied to the surface on which the resin coating film composed of the silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin, and a fluororesin is allowed to act. The metal foil according to any one of (21) to (24), wherein a chromate treatment is performed before the film is allowed to act.
(26) The metal foil according to any one of (21) to (25), wherein a ten-point average roughness (Rz jis) of a side surface in contact with the resin coating film of the metal foil is 3.5 μm or less.
(27) A resinous plate carrier having a resin coating film composed of silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin and a fluororesin on at least one surface .
(28) The plate-like carrier according to (27), wherein the resin coating film contains 10 to 1500 parts by mass of a total of epoxy resin and melamine resin with respect to 100 parts by mass of silicone.
(29) The plate carrier according to (27) or (28), wherein the resin coating film contains 0 to 50 parts by mass of a fluororesin with respect to 100 parts by mass of silicone.
(30) The plate-shaped carrier according to any one of (27) to (29), wherein the resin coating film has a thickness of 0.1 to 10 μm.
(31) A resinous plate-like carrier having a resin coating film composed of silicone and any one or a plurality of resins selected from epoxy resins, melamine resins and fluororesins on at least one surface And the plate-shaped carrier used for the use which adheres metal foil in the said surface so that peeling is possible.
(32) The plate-like carrier according to (31), wherein the resin coating film contains a total of 10 to 1500 parts by mass of epoxy resin and melamine resin with respect to 100 parts by mass of silicone.
(33) The plate-like carrier according to (31) or (32), wherein the resin coating film contains a fluororesin in an amount of 0 to 50 parts by mass with respect to 100 parts by mass of silicone.
(34) The plate-shaped carrier according to any one of (31) to (33), wherein the resin coating film has a thickness of 0.1 to 10 μm.
(35) A resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of (1) to (13), and then the resin or the metal foil is repeatedly laminated one or more times. The manufacturing method of the multilayer metal clad laminated board including this.
(36) A resin is laminated on the metal foil side of the metal foil with a carrier according to any one of (1) to (13), and then a resin, a single-sided or double-sided metal-clad laminate, or (1) to (13) A method for producing a multilayer metal-clad laminate comprising laminating a metal foil with a carrier according to any one of the above or a metal foil one or more times.
(37) The method for producing a multilayer metal-clad laminate according to (35) or (36), further comprising a step of peeling and separating the plate-like carrier and metal foil of the metal foil with carrier. A manufacturing method of a board.
(38) The method for producing a multilayer metal-clad laminate comprising the step of removing a part or all of the separated and separated metal foil by etching in the production method according to (37).
(39) A multilayer metal-clad laminate obtained by the production method according to any one of (35) to (38).
(40) A method for manufacturing a buildup substrate, comprising a step of forming one or more buildup wiring layers on the metal foil side of the metal foil with a carrier according to any one of (1) to (13).
(41) The buildup substrate manufacturing method according to (40), wherein the buildup wiring layer is formed by using at least one of a subtractive method, a full additive method, or a semi-additive method.
(42) A resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of (1) to (13), and then resin, single-sided or double-sided wiring board, single-sided or double-sided metal-clad laminate , (1) to (13) A method for producing a build-up substrate, comprising laminating the metal foil with a carrier or the metal foil according to any one of the above one or more times.
(43) In the method for manufacturing a build-up board according to (42), a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, a metal foil with a carrier, a plate-like carrier with a metal foil with a carrier, a metal foil Or a method for manufacturing a build-up substrate, further comprising the steps of drilling a hole in the resin and conducting conductive plating on the side and bottom surfaces of the hole.
(44) In the method for manufacturing a build-up board according to (42) or (43), a metal foil constituting the single-sided or double-sided wiring board, a metal foil constituting a single-sided or double-sided metal-clad laminate, and a metal foil with a carrier The manufacturing method of the buildup board | substrate which further includes performing the process of forming wiring in at least one of metal foil which comprises this, and at least 1 of metal foil.
(45) A step of contacting and laminating the resin plate side of the metal foil with carrier according to any one of (1) to (13), wherein the metal foil is adhered to one surface on the surface on which the wiring is formed. A method for manufacturing a build-up substrate according to any one of (42) to (44).
(46) One of the metal foils with a carrier according to any one of (1) to (13), wherein a resin is laminated on the surface on which the wiring is formed, and a metal foil is adhered to both sides of the resin. The method for manufacturing a buildup substrate according to any one of (42) to (44), further comprising a step of bringing the metal foil into contact with each other and laminating.
(47) The method for manufacturing a buildup substrate according to any one of (42) to (46), wherein at least one of the resins is a prepreg.
(48) The buildup wiring according to any one of (40) to (47), further comprising a step of peeling and separating the plate-like carrier and the metal foil of the metal foil with carrier. A manufacturing method of a board.
(49) The method for manufacturing a buildup wiring board according to (48), further comprising a step of removing a part or all of the metal foil adhered to the plate carrier by etching.
(50) A build-up wiring board obtained by the production method according to (48) or (49).
(51) A method for producing a printed circuit board, comprising a step of producing a build-up board by the production method according to any one of (40) to (47).
(52) A method for producing a printed circuit board, comprising a step of producing a build-up wiring board by the production method according to (48) or (49).

According to the present invention, the peel strength between the plate carrier and the metal foil can be easily adjusted. Therefore, for example, a metal foil with a carrier that has conventionally exhibited an excessively high peel strength is adjusted to a preferable peel strength, so that an advantage of improving the productivity of a printed wiring board using the metal foil with a carrier is obtained. .

An example of the configuration of CCL is shown. The structural example of the metal foil with a carrier which concerns on this invention is shown. The assembly example of the multilayer CCL using the copper foil with a carrier which concerns on this invention (The form which copper foil joined to the single side | surface of the resin board) is shown. The assembly example of the multilayer CCL using the copper foil with a carrier which concerns on this invention (The form which copper foil joined on both surfaces of the resin board) is shown.

In one embodiment of a metal foil with a carrier according to the present invention, a metal foil with a carrier comprising a resin-made plate-like carrier and a metal foil that is detachably adhered to one or both sides, preferably both sides of the carrier, is prepared. To do. One structural example of the metal foil with a carrier according to the present invention is shown in FIGS. In particular, the metal foil with carrier 11 in which the metal foil 11a is detachably adhered to both surfaces of a resin plate carrier 11c is shown at the beginning of FIG. The plate-like carrier 11c and the metal foil 11a are bonded together using a resin coating film 11b having a specific structure to be described later.

Although structurally similar to the CCL shown in FIG. 1, the metal foil with a carrier of the present invention has a structure in which the metal foil and the resin are finally separated and can be easily peeled off. In this respect, since the CCL is not peeled off, the structure and function are completely different.

Since the metal foil with carrier used in the present invention must be peeled off eventually, it is inconvenient that the adhesiveness is excessively high, but the plate-like carrier and the metal foil are chemicals such as plating performed in the printed circuit board manufacturing process. Adhesiveness that does not peel in the processing step is necessary.

Here, the peel strength between the metal foil provided by the resin coating film and the plate-like carrier is preferably 10 gf / cm or more, more preferably 30 gf / cm or more, and 50 gf / cm or more. Is more preferably 200 gf / cm or less, more preferably 150 gf / cm or less, and still more preferably 80 gf / cm or less. By making the peel strength between the metal foil and the plate carrier in such a range, the peel strength is such that it can be easily peeled off by hand, that is, mechanically peeled off, without being peeled off during transport or processing. Easy to adjust.

As described later, the adjustment of the peel strength for realizing such adhesion is composed of silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin, and a fluororesin. This is done by using a resin coating. Such a resin coating film is baked under predetermined conditions as will be described later, and bonded between the plate-like carrier and the metal foil, whereby the adhesiveness is moderately lowered and the peel strength is described above. This is because the range can be adjusted.

Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, brominated epoxy resin, amine type epoxy resin, flexible epoxy resin, hydrogenated bisphenol A type epoxy resin, phenoxy resin, Examples thereof include brominated phenoxy resin.

Examples of the melamine-based resin include methyl etherified melamine resin, butylated urea melamine resin, butylated melamine resin, methylated melamine resin, and butyl alcohol-modified melamine resin. The melamine resin may be a mixed resin of the resin and a butylated urea resin, a butylated benzoguanamine resin, or the like.

The number average molecular weight of the epoxy resin is preferably 2000 to 3000, and the number average molecular weight of the melamine resin is preferably 500 to 1000. By having such a number average molecular weight, the resin can be made into a paint and the adhesive strength of the resin coating film can be easily adjusted to a predetermined range.

Also, examples of the fluororesin include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride.

Examples of silicone include methylphenyl polysiloxane, methyl hydropolysiloxane, dimethyl polysiloxane, modified dimethyl polysiloxane, and mixtures thereof. Here, the modification is, for example, epoxy modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, fluorine modification, alkylaralkyl polyether modification, epoxy polyether modification, polyether modification, alkyl higher alcohol ester modification, polyester modification. And acyloxyalkyl modification, halogenated alkylacyloxyalkyl modification, halogenated alkyl modification, aminoglycol modification, mercapto modification, hydroxyl group-containing polyester modification, and the like.

In the resin coating film, if the film thickness is too small, the resin coating film is too thin and difficult to form, so that the productivity is likely to decrease. Moreover, even if a film thickness exceeds a fixed magnitude | size, the further improvement of the peelability of a resin coating film is not seen, but the manufacturing cost of a resin coating film tends to become high. From such a viewpoint, the resin coating film preferably has a thickness of 0.1 to 10 μm, and more preferably 0.5 to 5 μm. Moreover, the film thickness of a resin coating film is achieved by apply | coating a resin coating material by the predetermined application amount in the procedure mentioned later.

In the resin coating, silicone functions as a release agent for the resin coating. Therefore, if the total amount of epoxy resin and melamine resin is too much compared to silicone, the peel strength imparted by the resin coating between the plate-like carrier and the metal foil increases, so that the peelability of the resin coating is increased. May decrease and may not be easily removed by hand. On the other hand, if the total amount of the epoxy resin and the melamine resin is too small, the above-mentioned peel strength becomes small, and therefore, the metal foil with a carrier may be peeled off during transport or processing. From this viewpoint, the total of the epoxy resin and the melamine resin is preferably contained in an amount of 10 to 1500 parts by weight, more preferably 20 to 800 parts by weight with respect to 100 parts by weight of silicone. Is preferred.

Further, like silicone, fluororesin functions as a release agent and has the effect of improving the heat resistance of the resin coating film. If the amount of fluororesin is too much compared to silicone, the aforementioned peel strength will be low, which may cause peeling during transport or processing of the metal foil with carrier, and it will be uneconomical because the temperature required for the baking process described later will increase. It becomes. From this viewpoint, the fluororesin is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass with respect to 100 parts by mass of silicone.

The resin coating film is selected from SiO ₂ , MgO, Al ₂ O ₃ , BaSO ₄ and Mg (OH) ₂ in addition to silicone and epoxy resin and / or melamine resin and, if necessary, fluororesin 1 You may contain the surface roughening particle | grains more than a seed | species. When the resin coating film contains surface roughening particles, the surface of the resin coating film becomes uneven. Due to the unevenness, the surface of the plate-like carrier or metal foil to which the resin coating film is applied becomes uneven and becomes a matte surface. The content of the surface roughening particles is not particularly limited as long as the resin coating is roughened, but it is preferably 1 to 10 parts by mass with respect to 100 parts by mass of silicone.

The particle diameter of the surface roughened particles is preferably 15 nm to 4 μm. Here, the particle diameter means an average particle diameter (average value of the maximum particle diameter and the minimum particle diameter) measured from a scanning electron microscope (SEM) photograph or the like. When the particle diameter of the surface roughened particles is within the above range, the unevenness on the surface of the resin coating film can be easily adjusted, and as a result, the unevenness on the surface of the plate-like carrier or metal foil can be easily adjusted. Specifically, the amount of irregularities on the surface of the plate-like carrier or metal foil is about 4.0 μm in terms of the maximum height roughness Ry defined by JIS.

Here, the manufacturing method of metal foil with a carrier is demonstrated.
This metal foil with a carrier is obtained through a procedure having a step of applying the above-described resin coating to at least one surface of a plate-like carrier or metal foil and a baking step of curing the applied resin coating. . Hereinafter, each step will be described.

(Coating process)
In the coating process, a resin coating consisting of silicone as the main agent, epoxy resin as the curing agent, melamine resin, and fluororesin as the release agent as required is applied to one or both sides of the plate-like carrier. And forming a resin coating film. The resin paint is obtained by dissolving an epoxy resin, a melamine resin, a fluororesin, and silicone in an organic solvent such as alcohol. The blending amount (addition amount) in the resin coating is preferably 10 to 1500 parts by mass of the total of the epoxy resin and the melamine resin with respect to 100 parts by mass of the silicone. The fluororesin is preferably 0 to 50 parts by mass with respect to 100 parts by mass of silicone.

The coating method in the coating process is not particularly limited as long as a resin coating film can be formed, but a gravure coating method, a bar coating method, a roll coating method, a curtain flow coating method, a method using an electrostatic coating machine, etc. are used. In view of the uniformity of the resin coating film and the ease of work, the gravure coating method is preferred. The coating amount is preferably 1.0 to 2.0 g / m ² so that the resin coating film 3 has a preferable film thickness: 0.5 to 5 μm.

The gravure coating method is a method in which a resin coating film is formed on the surface of a plate-like carrier by transferring a resin coating filled in a recess (cell) provided on the roll surface to the plate-like carrier. Specifically, the lower part of the lower roll having cells provided on the surface is immersed in the resin paint, and the resin paint is pumped into the cell by the rotation of the lower roll. Then, the plate-like carrier is arranged between the lower roll and the upper roll arranged on the upper side of the lower roll, and the lower roll and the upper roll are held while pressing the plate-like carrier against the lower roll with the upper roll. By rotating, the plate-like carrier is conveyed, and the resin paint pumped into the cell is transferred (applied) to one side of the plate-like carrier.

In addition, by placing a doctor blade on the side where the plate-shaped carrier is brought into contact with the surface of the lower roll, excess resin paint pumped up on the roll surface other than the cells is removed, and the surface of the plate-shaped carrier is removed. A predetermined amount of resin paint is applied to the substrate. In addition, when the count (size and depth) of a cell is large, or when the viscosity of a resin coating is high, the resin coating film formed on one side of a plate-like carrier becomes difficult to become smooth. Therefore, a smoothing roll may be disposed on the carry-out side of the plate carrier to maintain the smoothness of the resin coating film.

In addition, when forming the resin coating film on both surfaces of the plate carrier, after forming the resin coating film on one surface of the plate carrier, turn over the plate carrier, and again between the lower roll and the upper roll. Place between. In the same manner as described above, the resin paint in the cell of the lower roll is transferred (applied) to the back surface of the plate-like carrier.

(Baking process)
The baking step is a step of subjecting the resin coating film formed in the coating step to a baking treatment at 125 to 320 ° C. (baking temperature) for 0.5 to 60 seconds (baking time). In this way, by subjecting the resin coating formed with a predetermined amount of resin coating to a predetermined baking condition, the peel strength between the plate carrier and the metal foil provided by the resin coating is in a predetermined range. Controlled. In the present invention, the baking temperature is the ultimate temperature of the plate carrier. Moreover, a conventionally well-known apparatus is used as a heating means used for a baking process.

When the baking is insufficient, for example, when the baking temperature is less than 125 ° C. or when the baking time is less than 0.5 seconds, the resin coating becomes insufficiently cured, and the peel strength exceeds 200 gf / cm, The peelability is reduced. Moreover, when baking is an excessive condition, for example, when baking temperature exceeds 320 degreeC, a resin coating film deteriorates, the said peeling strength exceeds 200 gf / cm, and the workability | operativity at the time of peeling deteriorates. Or a plate-shaped carrier may change in quality by high temperature. Further, when the baking time exceeds 60 seconds, the productivity is deteriorated.

In the method for producing a metal foil with a carrier, the resin coating in the coating step is made of silicone as a main agent, epoxy resin as a curing agent, melamine resin, fluororesin as a release agent, SiO ₂ , MgO, Al _It may be composed of one or more kinds of surface roughened particles selected from ₂ O ₃ , BaSO ₄ and Mg (OH) ₂ .

Specifically, the resin paint is obtained by further adding surface roughening particles to the above-described silicone-added resin solution. By further adding such surface-roughened particles to the resin coating, the surface of the resin coating film becomes uneven, and the unevenness makes the plate-like carrier or metal foil uneven, resulting in a matte surface. In order to obtain a plate-like carrier or metal foil having such a matte surface, the blending amount (addition amount) of surface roughening particles in the resin coating is 1 to 10 masses per 100 mass parts of silicone. Part. Further, it is more preferable that the surface roughened particles have a particle size of 15 nm to 4 μm.

The production method according to the present invention is as described above. However, in carrying out the present invention, other steps may be included between or before and after each step within a range that does not adversely affect each step. . For example, you may perform the washing | cleaning process which wash | cleans the surface of a plate-shaped carrier before an application | coating process.

Also, in the process of manufacturing a multilayer printed wiring board, heat treatment is often performed in a lamination press process or a desmear process. Therefore, the heat history that the metal foil with a carrier receives becomes severer as the number of laminated layers increases. Therefore, when considering application to a multilayer printed wiring board in particular, it is desirable that the peel strength between the metal foil provided by the resin coating film and the plate-like carrier is in the above-mentioned range even after passing through the required thermal history. .

Accordingly, in a further preferred embodiment of the present invention, the resin after heating at least one of 3 hours, 6 hours, or 9 hours, for example, at 220 ° C., assuming heating conditions in the production process of the multilayer printed wiring board. The peel strength between the metal foil provided by the coating film and the plate carrier is preferably 30 gf / cm or more, and more preferably 50 gf / cm or more. The peel strength is preferably 200 gf / cm or less, more preferably 150 gf / cm or less, and even more preferably 80 gf / cm or less.

Regarding the peel strength after heating at 220 ° C., the peel strength was described above in both 3 hours and 6 hours, or both 6 hours and 9 hours from the viewpoint of being able to cope with various lamination numbers. It is preferable to satisfy the range, and it is further preferable that all peel strengths after 3 hours, 6 hours, and 9 hours satisfy the above-described range.

In the present invention, the peel strength is measured in accordance with a 90 degree peel strength measuring method defined in JIS C6481.

Hereinafter, specific constituent requirements of each material for realizing such peel strength will be described.

The resin that serves as the plate-like carrier is not particularly limited, and phenol resin, polyimide resin, epoxy resin, natural rubber, pine resin, and the like can be used, but a thermosetting resin is preferable. A prepreg can also be used. The prepreg before being bonded to the metal foil is preferably in a B-stage state. The linear expansion coefficient of the prepreg (C stage) is 12 to 18 (× 10 ⁻⁶ / ° C.), 16.5 (× 10 ⁻⁶ / ° C.) of the copper foil as the constituent material of the substrate, or 17 of the SUS press plate .3 (× 10 ⁻⁶ / ° C.) is advantageous in that it is difficult to cause circuit misalignment due to a phenomenon (scaling change) in which the substrate size before and after pressing differs from that at the time of design. Furthermore, as a synergistic effect of these merits, it becomes possible to produce a multilayer ultra-thin coreless substrate. The prepreg used here may be the same as or different from the prepreg constituting the circuit board. Conventionally, a metal plate has been used as a plate-shaped carrier of a metal foil with a carrier. In this case, the plate-like carrier and the metal foil are adhered to each other by welding or adhesion. When using an adhesive, from the viewpoint of heat resistance, there are many things that are generally not suitable for build-up, and when closely contacting by welding, the peel strength is too high when using full-surface welding, It is difficult to peel off easily, and it becomes difficult to prevent the chemical solution from entering between the plate-shaped carrier and the metal foil when using partial welding. . Therefore, by using a resin-made plate-like carrier, an appropriate peel strength can be exhibited with the metal foil, and by using a heat-resistant resin, it can sufficiently withstand the heat history during build-up. be able to.

Therefore, the plate-like carrier preferably has a high glass transition temperature Tg from the viewpoint of maintaining the peel strength after heating in an optimal range, for example, a glass transition temperature Tg of 120 to 320 ° C., preferably 170 to 240 ° C. It is. The glass transition temperature Tg is a value measured by DSC (differential scanning calorimetry).

Also, it is desirable that the thermal expansion coefficient of the resin is within + 10% and −30% of the thermal expansion coefficient of the metal foil. As a result, it is possible to effectively prevent circuit misalignment due to the difference in thermal expansion between the metal foil and the resin, thereby reducing the occurrence of defective products and improving the yield.

The thickness of the plate-like carrier is not particularly limited and may be rigid or flexible. However, if it is too thick, it will adversely affect the heat distribution during hot pressing, while if it is too thin, it will bend and will not flow through the printed wiring board manufacturing process. Therefore, it is usually 5 μm or more and 1000 μm or less, preferably 50 μm or more and 900 μm or less, and more preferably 100 μm or more and 400 μm or less.

As the metal foil, copper or copper alloy foil is a typical one, but foil of aluminum, nickel, zinc or the like can also be used. In the case of copper or copper alloy foil, electrolytic foil or rolled foil can be used. Although not limited, the metal foil generally has a thickness of 1 [mu] m or more, preferably 5 [mu] m or more, and 400 [mu] m or less, preferably 120 [mu] m or less, considering use as a wiring of a printed circuit board. When metal foil is affixed on both surfaces of the plate-like carrier, metal foils having the same thickness may be used, or metal foils having different thicknesses may be used.

The metal foil used may be subjected to various surface treatments. For example, metal plating for the purpose of imparting heat resistance (Ni plating, Ni—Zn alloy plating, Cu—Ni alloy plating, Cu—Zn alloy plating, Zn plating, Cu—Ni—Zn alloy plating, Co—Ni alloy plating, etc. ), Chromate treatment (including the case where one or more alloy elements such as Zn, P, Ni, Mo, Zr, Ti, etc. are contained in the chromate treatment liquid) for imparting rust prevention and discoloration resistance, surface roughness (For example, copper electrodeposition grains, Cu—Ni—Co alloy plating, Cu—Ni—P alloy plating, Cu—Co alloy plating, Cu—Ni alloy plating, Cu—Co alloy plating, And copper alloy plating such as Cu—As alloy plating and Cu—As—W alloy plating). The roughening treatment not only affects the peel strength between the metal foil and the plate carrier, but also the chromate treatment has a great influence. Chromate treatment is important from the viewpoint of rust prevention and discoloration resistance, but since it tends to significantly increase the peel strength, it is also meaningful as a means for adjusting the peel strength.

In conventional CCL, since it is desired that the peel strength between the resin and the copper foil is high, for example, the matte surface (M surface) of the electrolytic copper foil is used as an adhesive surface with the resin, and surface treatment such as roughening treatment is performed. Thus, the adhesive strength is improved by the chemical and physical anchoring effects. On the resin side, various binders are added to increase the adhesive strength with the metal foil. As described above, in the present invention, unlike the CCL, since the metal foil and the resin need to be finally peeled, it is disadvantageous that the peel strength is excessively high.

Therefore, in a preferred embodiment of the metal foil with a carrier according to the present invention, the surface roughness of the bonded surface is JIS B 0601: in order to adjust the peel strength between the metal foil and the plate-like carrier to the preferred range described above. Expressed by the ten-point average roughness (Rz jis) of the metal foil surface measured according to 2001, it is preferably 3.5 μm or less, more preferably 3.0 μm or less. However, reducing the surface roughness indefinitely takes time and causes an increase in cost. Therefore, the surface roughness is preferably 0.1 μm or more, and more preferably 0.3 μm or more. When electrolytic copper foil is used as the metal foil, it is possible to use either a glossy surface (shiny surface, S surface) or a rough surface (matte surface, M surface) by adjusting to such a surface roughness. However, it is easier to adjust the surface roughness by using the S-plane. On the other hand, it is preferable that the ten-point average roughness (Rz jis) of the surface of the metal foil not contacting the carrier is 0.4 μm or more and 10.0 μm or less.

In a preferred embodiment of the metal foil with a carrier according to the present invention, the surface treatment for improving the peel strength such as roughening treatment is not performed on the bonding surface of the metal foil with the resin. Moreover, in preferable one Embodiment of metal foil with a carrier which concerns on this invention, the binder for improving the adhesive force with metal foil is not added in resin.

As conditions for hot pressing for producing a metal foil with a carrier, when a prepreg is used as a plate-like carrier, it is preferable to perform hot pressing at a pressure of 30 to 40 kg / cm ² and a temperature higher than the glass transition temperature of the prepreg. .

From the above viewpoints, the present invention applies the above-mentioned coupling agent to at least one surface of the metal foil as described above, which serves as the adhesion surface, in order to allow the resinous plate-like carrier to adhere in a peelable manner. Provide crafted metal foil. Further, the surface of the metal foil may be subjected to the chromate treatment as described above before applying the coupling agent.

From another viewpoint, the present invention provides a plate-like carrier having the above coupling agent on at least one surface of the plate-like carrier to be a close contact surface of the metal foil. This plate-like carrier can be suitably used for applications in which the metal foil as described above is adhered in a peelable manner.

From still another viewpoint, the present invention provides a metal foil for a coreless multilayer printed wiring board in which the above coupling agent is coated on the surface of the metal foil as described above. Further, the surface of the metal foil may be subjected to the chromate treatment as described above before being coated with the coupling agent.

The surface of the metal foil or resin was measured with a scanning electron microscope equipped with XPS (X-ray photoelectron spectrometer), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis), Al, If Ti and Zr are detected, it can be assumed that the coupling agent is present on the surface of the metal foil or resin.

Furthermore, from another viewpoint, this invention provides the use of the metal foil with a carrier mentioned above.
First, a multilayer metal comprising laminating a resin on at least one metal foil side of the above-described metal foil with carrier, and then laminating the resin or the metal foil repeatedly one or more times, for example, 1 to 10 times. A method for producing a tension laminate is provided.

Second, the resin is laminated on the metal foil side of the metal foil with carrier described above, and then the resin, single-sided or double-sided metal-clad laminate, or metal foil with carrier of the present invention, or metal foil once or more, for example, A method for producing a multilayer metal-clad laminate comprising repeatedly laminating 1 to 10 times is provided. In addition, the lamination after the resin laminated on the first metal foil with carrier is performed as many times as desired. In each lamination, a book different from the resin, single-sided or double-sided metal-clad laminate, and the first metal foil with carrier is used. It can be arbitrarily selected from the group consisting of the metal foil with carrier of the invention and the metal foil.

The above-described method for producing a multilayer metal-clad laminate can further include a step of peeling and separating the plate-like carrier and metal foil of the metal foil with carrier.

Further, the method may further include a step of removing a part or the whole of the metal foil by etching after the plate-like carrier and the metal foil are separated from each other.

Thirdly, a resin is laminated on the metal foil side of the metal foil with carrier described above, and then resin, single-sided or double-sided wiring board, single-sided or double-sided metal-clad laminate, or metal foil with carrier of the present invention, or metal foil Is provided one or more times, for example, 1 to 10 times, and a buildup substrate manufacturing method is provided. In addition, the lamination after the resin laminated on the first metal foil with carrier is performed as many times as desired. In each lamination, the resin, the single-sided or double-sided wiring board, the single-sided or double-sided metal-clad laminate, the first metal with carrier It can be arbitrarily selected from the group consisting of the metal foil with a carrier of the present invention different from the foil and the metal foil.

Fourth, there is provided a method for manufacturing a buildup board including a step of laminating one or more buildup wiring layers on the metal foil side of the metal foil with carrier described above. At this time, the build-up wiring layer can be formed using at least one of a subtractive method, a full additive method, and a semi-additive method.

The subtractive method is a method of forming a conductor pattern by selectively removing unnecessary portions of metal foil on a metal-clad laminate or a wiring board (including a printed wiring board and a printed circuit board) by etching or the like. Point to. The full additive method is a method of forming a conductor pattern by electroless plating and / or electrolytic plating without using a metal foil for the conductor layer. The semi-additive method is an electroless method on a seed layer made of metal foil, for example. In this method, a conductor pattern is formed by using metal deposition and electrolytic plating, etching, or a combination thereof, and then an unnecessary seed layer is removed by etching.

In the manufacturing method of the above build-up board, a hole is formed in a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, a metal foil with a carrier, a plate-like carrier with a metal foil with a carrier, a metal foil, or a resin. The method may further include a step of opening and conducting conductive plating on a side surface and a bottom surface of the hole. In addition, the step of forming wiring on at least one of the metal foil constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided metal-clad laminate, and the metal foil constituting the metal foil with carrier is performed once. It can further include performing the above.

The manufacturing method of the build-up board may further include a step of bringing a metal foil into close contact with one surface on the surface on which the wiring is formed, and further laminating the carrier side of the metal foil with a carrier according to the present invention. . Moreover, it is possible to further include a step of laminating a metal foil with a carrier according to the present invention in which a resin is laminated on the surface on which the wiring is formed and the metal foil is adhered to both sides of the resin.
The “surface on which the wiring is formed” means a portion where wiring is formed on the surface that appears every time a buildup is performed, and the buildup substrate includes both a final product and an intermediate product.

The manufacturing method of the build-up substrate may further include a step of peeling and separating the plate-like carrier of the metal foil with carrier and the metal foil.

Furthermore, it is possible to further include a step of removing a part or the whole surface of the metal foil by etching after peeling and separating the plate-like carrier and the metal foil.

In addition, in the manufacturing method of the above-mentioned multilayer metal-clad laminate and the manufacturing method of a buildup board, each layer can be laminated | stacked by performing thermocompression bonding. This thermocompression bonding may be performed every time one layer is stacked, may be performed after being laminated to some extent, or may be performed collectively at the end.

In particular, the present invention provides a method for manufacturing a build-up board as described above, wherein a hole is made in a single-sided or double-sided wiring board, a single-sided or double-sided copper-clad laminate, a metal foil or a resin, and conductive plating is performed on the side and bottom surfaces of the hole. Further, the metal foil and circuit portion constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided copper-clad laminate, and the method for producing a build-up board at least including the step of forming a circuit on the metal foil I will provide a.

Hereinafter, as a specific example of the above-described application, a method for producing a four-layer CCL using the metal foil with a carrier according to the present invention will be described. The metal foil with carrier used here is the metal foil with carrier 11 in which the metal foil 11a is adhered to one surface of the plate-like carrier 11c. A desired number of prepregs 12, then a two-layer printed circuit board or two-layer metal-clad laminate called an inner layer core 13, then a prepreg 12, and then a metal foil 11 with a carrier are sequentially stacked on the metal foil 11 with a carrier. A set of four-layer CCL assembly units is completed. Next, the unit 14 (referred to as “page”) is repeated about 10 times to form a press assembly 15 (referred to as “book”) (FIG. 3). Thereafter, the book 15 is sandwiched between the laminated molds 10 and set in a hot press machine, and a large number of four-layer CCLs can be manufactured simultaneously by press molding at a predetermined temperature and pressure. As the laminated mold 10, for example, a stainless plate can be used. Although the plate is not limited, for example, a thick plate of about 1 to 10 mm can be used. In general, CCL having four or more layers can be produced in the same process by increasing the number of inner core layers.

Hereinafter, as a specific example of the above-described application, a method for producing a coreless buildup substrate using the metal foil with carrier 11 in which the metal foil is in close contact with both surfaces of the plate-like carrier 11c of the resin plate according to the present invention will be described. . In this method, after a required number of buildup layers 16 are laminated on both sides of the metal foil with carrier 11, the metal foils on both sides are peeled from the metal foil with carrier 11 (see FIG. 4).

For example, on the metal foil side of the metal foil with a carrier of the present invention, a resin as an insulating layer, a two-layer circuit board, a resin as an insulating layer are stacked in order, and the metal foil side is in contact with the resin plate on it, Furthermore, a buildup board | substrate can be manufactured by laminating | stacking the metal foil of the metal foil with a carrier of this invention in order.

As another method, a resin or conductor layer as an insulating layer is provided on at least one metal foil side of the metal foil with a carrier in which the metal foil is adhered to both surfaces or one surface of the resinous plate-like carrier 11c. Are laminated in order. Next, if necessary, a step of half-etching the entire surface of the metal foil to adjust the thickness may be included. Next, laser processing is performed at a predetermined position of the laminated metal foil to form a via hole penetrating the metal foil and the resin, and after applying a desmear process for removing smear in the via hole, the bottom of the via hole, the side surface and the metal foil Electroless plating is performed on the entire surface or a part of the substrate to form an interlayer connection, and further electrolytic plating is performed as necessary. A plating resist may be formed in advance on each portion of the metal foil where electroless plating or electrolytic plating is unnecessary before performing each plating. In addition, when the electroless plating, the electrolytic plating, or the adhesion between the plating resist and the metal foil is insufficient, the surface of the metal foil may be chemically roughened in advance. When a plating resist is used, the plating resist is removed after plating. Next, a circuit is formed by removing unnecessary portions of the metal foil and the electroless plating portion and the electrolytic plating portion by etching. Thereby, a build-up substrate is obtained. The process from the lamination of the resin and metal foil to the circuit formation may be repeated a plurality of times to form a multilayer build-up substrate.
Furthermore, on the outermost surface of this buildup substrate, the resin side of the metal foil of the metal foil with a carrier in which the metal foil is adhered to one side of the present invention may be contacted and laminated, or a resin plate is once laminated. Later, one metal foil of the metal foil with a carrier in which the metal foil is adhered to both surfaces of the present invention may be brought into contact with each other and laminated.

Here, a prepreg containing a thermosetting resin can be suitably used as the resin plate used for manufacturing the build-up substrate.

As another method, a resin as an insulating layer such as a prepreg or a photosensitive layer is formed on the exposed surface of a metal foil of a laminate obtained by laminating a metal foil such as a copper foil on one or both sides of the plate carrier of the present invention. Laminating resin. Thereafter, a via hole is formed at a predetermined position of the resin. For example, when a prepreg is used as the resin, the via hole can be formed by laser processing. After the laser processing, desmear treatment for removing smear in the via hole is preferably performed. When a photosensitive resin is used as the resin, the resin in the via hole forming portion can be removed by a photolithography method. Next, electroless plating is performed on the bottom and side surfaces of the via holes, the entire surface or a part of the resin to form interlayer connections, and further electrolytic plating is performed as necessary. A plating resist may be formed in advance on each portion of the resin where electroless plating or electrolytic plating is unnecessary before performing each plating. Further, when the adhesion between electroless plating, electrolytic plating, plating resist and resin is insufficient, the surface of the resin may be chemically roughened in advance. When a plating resist is used, the plating resist is removed after plating. Next, an unnecessary portion of the electroless plating portion or the electrolytic plating portion is removed by etching to form a circuit. Thereby, a build-up substrate is obtained. The steps from resin lamination to circuit formation may be repeated a plurality of times to form a multilayered build-up substrate.
Further, the outermost surface of this build-up substrate is laminated by contacting the resin side of the laminate in which the metal foil is closely attached to one side of the present invention, or the resin side of the metal foil with a carrier having the metal foil closely attached to one side. Alternatively, after laminating the resin once, one metal foil of the laminate in which the metal foil is adhered to both surfaces of the present invention, or one metal foil of the metal foil with a carrier in which the metal foil is adhered to both surfaces May be laminated in contact with each other.

For the coreless build-up substrate manufactured in this way, a wiring is formed on the surface through a plating process and / or an etching process, and further, build-up wiring is performed by separating and separating between the carrier resin and the metal foil. The board is completed. Wiring may be formed on the peeling surface of the metal foil after peeling and separation, or the entire surface of the metal foil may be removed by etching to form a build-up wiring board. Furthermore, a printed circuit board is completed by mounting electronic components on the build-up wiring board. Moreover, a printed circuit board can be obtained even if an electronic component is mounted directly on a coreless buildup substrate before resin peeling.

Experimental examples are shown below as examples and comparative examples of the present invention, but these examples are provided for better understanding of the present invention and its advantages, and are intended to limit the invention. is not.

(Metal foil with carrier)
<Experimental Examples 1 to 10>
A plurality of electrolytic copper foils (thickness 12 μm, rough surface roughness Rz jis 3.7 μm) were prepared, and nickel-zinc (Ni—) according to the following conditions was applied to the shiny (glossy) surface of each electrolytic copper foil. Zn) alloy plating treatment and chromate (Cr—Zn chromate) treatment were performed, and the ten-point average roughness (Rz cis: measured in accordance with JIS B 0601: 2001) of the bonded surface (here, S surface) was 1. After setting the thickness to 5 μm, a prepreg (FR-4 resin: glass transition temperature Tg = 140 ° C .; thickness 200 μm) manufactured by Nanya Plastic Co., Ltd. was bonded to the S surface of the electrolytic copper foil as a resin and hot pressed at 170 ° C. for 100 minutes. The copper foil with a carrier was produced.

(Nickel-zinc alloy plating)
Ni concentration 17g / L (added as NiSO ₄ )
Zn concentration 4g / L (added as ZnSO ₄ )
pH 3.1
Liquid temperature 40 ℃
Current density 0.1-10A / dm ²
Plating time 0.1 to 10 seconds

(Chromate treatment)
Cr concentration 1.4g / L (added as CrO ₃ or K ₂ CrO ₇ )
Zn concentration 0.01 to 1.0 g / L (added as ZnSO ₄ )
Na ₂ SO ₄ concentration 10 g / L
pH 4.8
Liquid temperature 55 ℃
Current density 0.1-10A / dm ²
Plating time 0.1 to 10 seconds

In Experimental Examples 1 to 10, the glossy surface or the plate-like carrier (prepreg) was coated with a resin coating film having the structure shown in Table 1 and baked, and then the prepreg and copper foil were bonded together. It was.

The resin coating was applied using a gravure coating method, and then the thickness of the resin coating was adjusted to 2 to 4 μm using a doctor blade. The epoxy resin shown in Table 1 is a bisphenol A type epoxy resin, the melamine resin is a methyl etherified melamine resin, the fluororesin is polytetrafluoroethylene, and the dimethyl silicone resin is dimethyl Polysiloxane was used.
Moreover, the applied resin coating film was baked by heating at 150 ° C. for 30 seconds.

Further, assuming that some of the copper foils with a carrier have a thermal history during further heat treatment such as circuit formation on the copper foil with a carrier, the conditions described in Table 1 (here , 220 ° C. for 3 hours, 6 hours, and 9 hours).

The copper foil with a carrier obtained by hot pressing, and the copper foil with a carrier after the respective heat treatments for 3 hours, 6 hours, and 9 hours, and the plate-like carrier (resin after heating) The peel strength was measured. The results are shown in Table 1.

Also, in order to evaluate the peeling workability, the work time (hour / piece) by hand per unit number was evaluated. The results are shown in Table 2.

<Experimental example 11>
In Experimental Example 1, when the copper foil and the prepreg were bonded together, the carrier-coated copper was used under the same conditions as in Experimental Example 1, except that neither the glossy surface of the copper foil nor the prepreg was treated with a resin coating film. A foil was prepared, and the peel strength at each stage and the working time were evaluated. The respective results are shown in Table 1 and Table 2.

According to the table, the resin coating can be processed on the surface of the copper foil or the surface of the plate-like carrier (prepreg), and then the peel strength of the laminate, the peel strength after heating, and the peel It can be seen that the same results were obtained in workability.

(Build-up wiring board)
FR-4 prepreg (manufactured by Nanya Plastic Co., Ltd.) and copper foil (manufactured by JX Nippon Mining & Metals Co., Ltd., JTC 12 μm (product name)) are sequentially stacked on both sides of the copper foil with a carrier thus produced. A four-layer copper clad laminate was produced by hot pressing under the heating conditions shown in each table under the pressure of.

Next, a 100 μm diameter hole penetrating the copper foil on the surface of the four-layer copper-clad laminate and the insulating layer (cured prepreg) thereunder was drilled using a laser processing machine. Subsequently, electroless copper plating on the copper foil surface on the copper foil with carrier exposed at the bottom of the hole, the side surface of the hole, and the copper foil on the surface of the four-layer copper-clad laminate, and copper plating by electrolytic copper plating The electrical connection was formed between the copper foil on the copper foil with a carrier and the copper foil on the surface of the four-layer copper-clad laminate. Next, a part of the copper foil on the surface of the four-layer copper-clad laminate was etched using a ferric chloride-based etchant to form a circuit. In this way, a four-layer buildup substrate was obtained.

Subsequently, in the 4-layer build-up board, the two-layer build-up wiring boards were obtained by peeling off and separating the plate-like carrier of the copper foil with carrier and the copper foil.

Subsequently, the copper foil that was in close contact with the plate-like carrier on the two sets of two-layer build-up wiring boards was etched to form a wiring to obtain two sets of two-layer build-up wiring boards. .

In each experimental example, a plurality of four-layer build-up substrates were produced, and for each, the degree of contact between the prepreg and the copper foil constituting the copper foil with carrier in the build-up substrate manufacturing process was confirmed visually. In a build-up wiring board using a copper foil with a carrier manufactured under conditions where the peel strength and the peel strength after heating are evaluated as “G”, the resin (plate carrier) of the copper foil with a carrier is destroyed during the build-up. It was able to peel without being.
As for the condition evaluated as “N”, the resin was destroyed at the time of build-up during the peeling operation of the copper foil in the carrier-attached copper foil, or the resin remained on the copper foil surface without being peeled off.
As for the conditions evaluated as “-”, the resin was peeled off without being destroyed during the copper foil peeling operation in the carrier-added copper foil during build-up, but the copper foil was removed without peeling operation. Sometimes peeled off.

DESCRIPTION OF SYMBOLS 10 Laminated metal mold 11 Metal foil 11a with a carrier Metal foil 11b Resin coating film 11c Plate carrier 12 Prepreg 13 Inner core 14 Page 15 Book 16 Build-up layer

Claims

A metal foil with a carrier made of a resin-made plate-like carrier and a metal foil that is releasably adhered to at least one surface of the carrier, wherein the plate-like carrier and the metal foil are made of silicone, epoxy resin Metal foil with a carrier formed by bonding using a resin coating film composed of any one or a plurality of resins selected from melamine resins and fluororesins.
The metal foil with a carrier according to claim 1, wherein in the resin coating film, the total amount of epoxy resin and melamine resin is contained in an amount of 10 to 1500 parts by mass with respect to 100 parts by mass of silicone.
The metal foil with a carrier according to claim 1 or 2, wherein the resin coating contains 0 to 50 parts by mass of a fluororesin with respect to 100 parts by mass of silicone.
The metal foil with a carrier according to any one of claims 1 to 3, wherein the thickness of the resin coating film is 0.1 to 10 µm.
The metal foil with a carrier according to any one of claims 1 to 4, wherein the peel strength between the plate-like carrier and the metal foil is 10 gf / cm or more and 200 gf / cm or less.
The metal foil with a carrier according to any one of claims 1 to 5, wherein the resinous plate-like carrier contains a thermosetting resin.
The metal foil with a carrier according to any one of claims 1 to 6, wherein the resinous plate-like carrier is a prepreg.
The metal foil with a carrier according to claim 6 or 7, wherein the resinous plate-like carrier has a glass transition temperature Tg of 120 to 320 ° C.
The metal foil with a carrier according to any one of claims 1 to 8, wherein a ten-point average roughness (Rz jis) of a side surface in contact with the carrier of the metal foil is 3.5 µm or less.
The metal with a carrier according to any one of claims 1 to 9, wherein a ten-point average roughness (Rz jis) of a surface of the metal foil not contacting the carrier is 0.4 μm or more and 10.0 μm or less. Foil.
The metal foil with a carrier according to any one of claims 1 to 9, wherein the thickness of the metal foil is 1 µm or more and 400 µm or less.
The peel strength between the metal foil and the plate-like carrier after heating at 220 ° C. for 3 hours, 6 hours or 9 hours is 10 gf / cm or more and 200 gf / cm or less. A metal foil with a carrier according to claim 1.
The metal foil with a carrier according to any one of claims 1 to 12, wherein the metal foil is a copper foil.
Metal foil for printed wiring board having a resin coating film composed of silicone and any one or a plurality of resins selected from epoxy resins, melamine resins and fluororesins on the surface of the metal foil.
The metal foil for a printed wiring board according to claim 14, wherein the resin coating film includes 10 to 1500 parts by mass of a total of epoxy resin and melamine resin with respect to 100 parts by mass of silicone.
The metal foil for printed wiring board according to claim 14 or 15, wherein the resin coating film contains 0 to 50 parts by mass of a fluororesin with respect to 100 parts by mass of silicone.
The metal foil for printed wiring boards according to any one of claims 14 to 16, wherein the resin coating film has a thickness of 0.1 to 10 µm.
The resin coating acts on the surface on which the resin coating composed of the silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin, and a fluororesin is allowed to act. The metal foil for a printed wiring board according to any one of claims 14 to 17, wherein the metal foil is subjected to a chromate treatment before being made.
The metal foil for printed wiring board according to any one of claims 14 to 18, wherein a ten-point average roughness (Rz jis) of a side surface in contact with the resin coating film of the metal foil is 3.5 µm or less.
The print according to any one of claims 14 to 19, wherein a ten-point average roughness (Rz jis) of a surface of the metal foil not contacting the resin coating is 0.4 μm or more and 10.0 μm or less. Metal foil for wiring boards.
At least one surface is a metal foil having a resin coating film composed of silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin and a fluororesin, A metal foil used for the purpose of releasably attaching a resinous plate carrier.
The metal foil according to claim 21, wherein in the resin coating film, the total amount of epoxy resin and melamine resin is contained in an amount of 10 to 1500 parts by mass with respect to 100 parts by mass of silicone.
The metal foil according to claim 21 or 22, wherein the resin coating film contains a fluororesin in an amount of 0 to 50 parts by mass with respect to 100 parts by mass of silicone.
The metal foil according to any one of claims 21 to 23, wherein the thickness of the resin coating film is 0.1 to 10 µm.
The resin coating acts on the surface on which the resin coating composed of the silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin, and a fluororesin is allowed to act. The metal foil according to any one of claims 21 to 24, wherein the metal foil is subjected to a chromate treatment before being made.
The metal foil according to any one of claims 21 to 25, wherein a ten-point average roughness (Rz jis) of a side surface in contact with the resin coating film of the metal foil is 3.5 µm or less.
A resinous plate carrier having a resin coating film composed of silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin and a fluororesin on at least one surface.
The plate-shaped carrier according to claim 27, wherein the resin coating film contains a total of 10 to 1500 parts by mass of an epoxy resin and a melamine resin with respect to 100 parts by mass of silicone.
29. The plate carrier according to claim 27 or 28, wherein the resin coating film contains a fluororesin in an amount of 0 to 50 parts by mass with respect to 100 parts by mass of silicone.
The plate-like carrier according to any one of claims 27 to 29, wherein the resin coating film has a thickness of 0.1 to 10 µm.
A resinous plate-like carrier having, on at least one surface, a resin coating film composed of silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin, and a fluororesin A plate-like carrier used for applications in which the metal foil is peelably adhered on the surface.
The plate-like carrier according to claim 31, wherein the resin coating film contains a total of 10 to 1500 parts by mass of an epoxy resin and a melamine resin with respect to 100 parts by mass of silicone.
The plate-shaped carrier according to claim 31 or 32, wherein the resin coating contains a fluororesin in an amount of 0 to 50 parts by mass with respect to 100 parts by mass of silicone.
The plate carrier according to any one of claims 31 to 33, wherein the thickness of the resin coating film is 0.1 to 10 µm.
A multilayer comprising laminating a resin on at least one metal foil side of the metal foil with a carrier according to any one of claims 1 to 13, and then repeatedly laminating the resin or the metal foil one or more times. A method for producing a metal-clad laminate.
A resin is laminated on the metal foil side of the metal foil with a carrier according to any one of claims 1 to 13, and then a resin, a single-sided or double-sided metal-clad laminate, or any one of claims 1 to 13. A method for producing a multilayer metal-clad laminate comprising laminating a metal foil with a carrier as described in 1 or a metal foil one or more times.
37. The method for producing a multilayer metal-clad laminate according to claim 35 or 36, further comprising a step of peeling and separating the plate-like carrier and metal foil of the metal foil with carrier.
38. The method for producing a multilayer metal-clad laminate according to claim 37, comprising a step of removing a part or all of the separated and separated metal foil by etching.
A multilayer metal-clad laminate obtained by the production method according to any one of claims 35 to 38.
A method for manufacturing a buildup board, comprising a step of forming one or more buildup wiring layers on the metal foil side of the metal foil with a carrier according to any one of claims 1 to 13.
41. The method for manufacturing a build-up board according to claim 40, wherein the build-up wiring layer is formed by using at least one of a subtractive method, a full additive method, and a semi-additive method.
A resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of claims 1 to 13, and then a resin, a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, 14. A method for producing a build-up substrate, comprising: laminating the metal foil with a carrier according to any one of 1 to 13 or the metal foil repeatedly one or more times.
43. The build-up board manufacturing method according to claim 42, wherein the single-sided or double-sided wiring board, the single-sided or double-sided metal-clad laminate, the metal foil of the metal foil with carrier, the plate carrier of the metal foil with carrier, the metal foil, or the resin The manufacturing method of the buildup board | substrate which further includes the process of drilling a hole in and carrying out conductive plating to the side and bottom face of the said hole.
44. The method of manufacturing a build-up board according to claim 42 or 43, wherein the metal foil constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided metal-clad laminate, or the metal foil constituting the metal foil with carrier And the manufacturing method of the buildup board | substrate which further includes performing the process of forming wiring in at least one of metal foil once or more.
14. The method according to claim 1, further comprising the step of contacting and laminating the resin plate side of the metal foil with a carrier according to any one of claims 1 to 13, wherein the metal foil is adhered to one surface on the surface on which the wiring is formed. 45. A method of manufacturing a build-up substrate according to any one of 42 to 44.
The metal foil with carrier according to any one of claims 1 to 13, wherein a resin is laminated on the surface on which the wiring is formed, and the metal foil is adhered to both sides of the resin. The method for producing a build-up substrate according to any one of claims 42 to 44, further comprising a step of laminating the layers.
The method for manufacturing a buildup substrate according to any one of claims 42 to 46, wherein at least one of the resins is a prepreg.
The buildup wiring board manufacturing method according to any one of claims 40 to 47, further comprising a step of peeling and separating the plate-like carrier of the metal foil with carrier and the metal foil. Method.
49. The method for manufacturing a buildup wiring board according to claim 48, further comprising a step of removing a part or all of the metal foil adhered to the plate carrier by etching.
A build-up wiring board obtained by the manufacturing method according to claim 48 or 49.
A method for producing a printed circuit board, comprising a step of producing a build-up substrate by the production method according to any one of claims 40 to 47.
A method for manufacturing a printed circuit board, comprising a step of manufacturing a build-up wiring board by the manufacturing method according to claim 48 or 49.